Cyclic voltammetry (CV) and in-situ electronic conductivity curves have been simultaneously measured during Li-ion Insertion de-insertion Into from thin, partially crystallized. Li8V2O5 film in 1 M LiBF4+ propylene carbonate solution. A similarity has been observed between the CV curves and the plots of the derivative of conductivity, d sigma/dE, versus potential. A semi-metal-to-insulator transition. and vice versa, has been observed (in intercalation and de-intercalation, respectively), ascribed to the epsilon- to delta-phase transition of LixV2O5. This transition Is accompanied by an increase in the V-V distance between adjacent VO8; layers. and is probably responsible for the decrease in the film conductivity, realized via electron hopping between the high and low-valence vanadium sites.